WO1995020002A1 - Two-part polyurethane adhesive with improved adhesive power - Google Patents

Two-part polyurethane adhesive with improved adhesive power Download PDF

Info

Publication number
WO1995020002A1
WO1995020002A1 PCT/EP1995/000089 EP9500089W WO9520002A1 WO 1995020002 A1 WO1995020002 A1 WO 1995020002A1 EP 9500089 W EP9500089 W EP 9500089W WO 9520002 A1 WO9520002 A1 WO 9520002A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
polyol
oleochemical
polyurethane adhesives
mixtures
Prior art date
Application number
PCT/EP1995/000089
Other languages
German (de)
French (fr)
Inventor
Bernhard Grünewälder
Peter Daute
Johann Klein
Michael Dziallas
Wilfried Hübner
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to AT95905620T priority Critical patent/ATE209224T1/en
Priority to EP95905620A priority patent/EP0740675B1/en
Priority to DK95905620T priority patent/DK0740675T3/en
Priority to DE59509867T priority patent/DE59509867D1/en
Publication of WO1995020002A1 publication Critical patent/WO1995020002A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes

Definitions

  • the invention relates to a two-component polyurethane adhesive with improved adhesive properties, which contains polyols based on renewable raw materials as the polyol component.
  • Polyurethane adhesives have been known and widely used for years. Of particular importance, especially in technical applications, are the two-component adhesives which are mixed by the user prior to bonding to form a reaction mixture which then hardens after application to the substrates to be bonded.
  • Such two-component adhesives consist of a polyol component and an isocyanate component with functionality 2 and higher.
  • Suitable polyols based on renewable raw materials include castor oil or the oleochemical polyols described in DE-Al 33 47 045, which essentially consist of Reaction of epoxidized fatty substances with alcohols are accessible.
  • the adhesives produced according to the teaching of DE-Al 33 47 045 have the disadvantage that they do not have a high adhesive strength under climatic conditions with high atmospheric humidity or when exposed to condensation water. According to the teaching of DE-Al 40 41 119, this deficiency should be remedied by the fact that polyfunctional, non-saponifiable alcohols, which are obtained by ring-opening reaction of epoxidized internal olefins or epoxidized fatty alcohols, alone or in admixture with low molecular weight diols or Triplets can be added to the polyols based on renewable raw materials in amounts of 3 to 50% by weight based on the polyurethane formed. As can be seen from the examples given there, this means that preferably 33% by weight based on the polyol, in a minimal case 11% by weight based on the polyol, are used.
  • the alcohols mentioned can only be prepared by complex processes, for example an unsaturated one first Epoxidized fatty alcohol and then subjected to a ring opening.
  • the object of the invention was to provide an easy-to-carry out method by adding diols or diol mixtures and / or trifunctional hydroxyl compounds or mixtures thereof with certain hydroxyl numbers in certain amounts to the polyol component, with which the adhesive strength of Two-component polyurethane adhesives containing oleochemical polyols, especially under moist conditions, can be improved.
  • the invention relates to two-component polyurethane adhesives based on a) a polyol component containing oleochemical polyols, and b) an isocyanate component in which component a) comprises 2 to 7% by weight of difunctional and / or trifunctional alcohols or mixtures thereof on the oleochemical polyol - and that the hydroxyl number of the alcohols or their mixtures is 1100 to 1850.
  • Another object of the invention is an oleochemical polyol-containing polyol component for the production of polyurethanes, which additionally contains 2 to 7% by weight of difunctional and / or trifunctional alcohols or their mixtures with hydroxyl numbers between 1100 and 1850, based on the oleochemical polyol.
  • Another object of the invention relates to the use of two-component polyurethane adhesives for bonding rigid or flexible substrates, in particular plastics, metals, glass or, particularly preferably, wood to one another or to one another.
  • Diols or diol mixtures which can be used are diols having hydroxyl numbers from 1100 to 1500, preferably 1150 to 1350, particularly preferably 1200 to 1300, for example 1,2-propanediol, 1,3-propanediol, 2,3-butanediol or 1,4-butenediol. 1,4-Butanediol is particularly preferably used.
  • diol mixtures with hydroxyl numbers from 1100 to 1500 preferably 1150 to 1350, particularly preferably 1200 to 1300 can also be used. It is not necessary for the constituents of the mixture to have hydroxyl numbers in the range mentioned, rather it is also possible to use a mixture of diols which individually have hydroxyl numbers below 1100 or above 1500, e.g. of mixtures of 1,2-ethanediol and 1,6-hexanediol which fall in the hydroxyl number range from 1100 to 1500.
  • trifunctional hydroxyl compounds with hydroxyl numbers from 1100 to 1850 can be used, e.g. Trimethylolpropane, trimethylolethane or the addition product of 1 mol ethylene oxide with glycerol. Glycerin is particularly preferably used.
  • the amounts of the diols or diol mixtures and / or the trifunctional hydroxyl compounds or their mixtures are between 2 and 7% by weight, preferably between 4 and 6% by weight, based on the polyol.
  • the polyols of the polyurethane adhesives according to the invention can be oleochemical polyols. Oleochemical polyols are understood to mean polyols based on natural oils and fats, for example the reaction products of epoxidized fatty substances with mono-, di- or polyfunctional alcohols or glycerol esters of long-chain fatty acids which are at least partially substituted with hydroxyl groups.
  • a subgroup of these compounds are the ring opening products of epoxidized triglycerides, ie epoxidized fatty acid glycerol esters, in which the ring opening has been carried out while maintaining the ester bonds.
  • epoxidized triglycerides of vegetable or animal origin can be used to produce the ring opening products.
  • epoxidized triglycerides are suitable which have 2 to 10 percent by weight of epoxy oxygen.
  • Such products can be made by epoxidation of the double bonds from a range of fats and oils, e.g. Beef tallow, palm oil, peanut oil, turnip oil, cottonseed oil, soybean oil, sunflower oil and linseed oil.
  • Particularly preferred epoxidized triglycerides are epoxidized soybean oil and epoxidized linseed oil.
  • alcohols for the ring opening of the epoxidized triglycerides methanol, ethanol, propanol, isopropanol, butanol, hexanol, 2-ethylhexanol, fatty alcohols with 6 to 22 carbon atoms, cyclohexanol, benzyl alcohol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentylglycol, trimethylolpropane, glycerol, trimethylolethane, pentaerythritol, sorbitol and those containing ether groups Hydroxy compounds such as alkyl glycols or oligomeric glycols and oligomeric glycerols can be used.
  • epoxidized fatty acid esters or triglycerides with an alcohol can optionally be followed by a transesterification with itself or other subsequently added triglycerides, such as palm oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, sunflower oil and linseed oil.
  • triglycerides such as palm oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, sunflower oil and linseed oil.
  • Such oleochemical polyols are e.g. described in German patent application DE-Al 41 28 649.
  • oleochemical polyols are ring opening and transesterification products of epoxidized fatty acid esters of lower alcohols, ie of epoxidized fatty acid methyl, ethyl, propyl or butyl esters.
  • the ring opening or transesterification products with alcohols of functionality 2 to 4 are preferred here, in particular the reaction products with ethylene glycol, propylene glycol 1, oligomeric ethylene glycols, oligomeric propylene glycols, glycerol, trimethylolpropane or pentaerythritol.
  • Such products can be produced by known epoxidation or ring-opening processes, and the transesterification can be carried out during or after the ring-opening step by removing the lower alcohol from the reaction equilibrium.
  • Ring opening and transesterification products are preferred, in which a molar ratio between epoxidized fatty acid ester and the alcohol used for the reaction of 1: 1 to 1:10 has been used.
  • the oleochemical polyols also include the reaction products of epoxidized fatty alcohols with C2-C8 alcohols functionality 1 to 10, in particular 2 to 4, in the molar ratio of the epoxy groups to the hydroxyl groups from 1: 1 to 1:10.
  • oleochemical polyols which are obtained via the transesterification of di- or polyfunctional alcohols, e.g. the addition product of ethylene oxide or propylene oxide to glycerol with triglycerides, e.g. Palm oil, peanut oil, turnip oil, cottonseed oil, soybean oil, sunflower oil and linseed oil are accessible.
  • triglycerides e.g. Palm oil, peanut oil, turnip oil, cottonseed oil, soybean oil, sunflower oil and linseed oil are accessible.
  • polyols which, according to the teaching of DE-A1 41 24 665, can be obtained by transesterifying polymerized glycerol with the abovementioned triglycerides.
  • the polyols can have hydroxyl numbers from 50 to 400, preferably 100 to 300.
  • castor oil as an oleochemical polyol is particularly preferred.
  • the second component of the adhesives according to the invention can contain an isocyanate compound with the functionality of 2 to 4.
  • aromatic and aliphatic, monocyclic and polycyclic, multifunctional isocyanate compounds are suitable.
  • Suitable aromatic di- or higher-functional isocyanates are 2,4-tolylene diisocyanate, 2,6- Toluene diisocyanate or its mixtures, diphenylmethane diisocyanate or its technical qualities that contain higher-functional isocyanates.
  • Aliphatic isocyanates of functionality 2 and higher are preferably used, for example isophorone diisocyanate, trimerized isophorone diisocyanate or isocyanurate groups or 1,6-hexane diisocyanate, trimerized 1,6-hexane diisocyanate containing biuret groups and dicyclohexylmethane diisocyanate.
  • a modified, trimerized 1,6-hexanediisocyanate is used as the aliphatic isocyanate compound, which is commercially available under the name "Desmodur ( R ) DA” (Bayer AG, Leverkusen, FRG).
  • adducts of polyfunctional isocyanates with polyfunctional alcohols such as the reaction products of one of the aforementioned aromatic or aliphatic diisocyanates with, for example, ethylene glycol, propylene glycol, glycerol, trimethylolpropane or pentaerythritol, can also be used as isocyanates in the two-component polyurethane adhesives according to the invention.
  • reaction products of diisocyanates with polyether polyols e.g. Polyether polyols based on polypropylene oxide can be used as the isocyanate component.
  • the ratio of the isocyanate groups contained in the isocyanate component to the OH groups contained in the polyol component is generally in the range of equivalence, ie the NCO: OH ratio is between 1.1 and 0.9, preferably around 1.0.
  • the two-component polyurethane adhesives according to the invention can furthermore contain various auxiliaries, which are preferably added to the polyol component.
  • organic fillers can also be used, in particular fiber short cuts, hollow plastic spheres and others. Fillers are preferred which impart thixotropy to the adhesive mixtures.
  • the polyurethane adhesives according to the invention may also contain other auxiliaries.
  • Plasticizers, flame retardants, retarders, dyes and anti-aging agents such as are known in corresponding adhesives are to be mentioned.
  • Solvents which do not react with the isocyanate groups, such as esters, ketones and aromatic hydrocarbons, can also be used, although not preferred.
  • the auxiliaries can be contained in amounts of 0.1 to 75% by weight, based on the adhesive.
  • the adhesives according to the invention can furthermore contain accelerators.
  • Suitable are, for example, tertiary bases such as Bis- (, N-dimethylamino) diethyl ether, N, N-dimethylbenzylamine, N-methylmorpholine and the reaction products of dialkyl- ( ⁇ -hydroxyethyl) amines with monoisocyanates and esterification products of these amines with dicarboxylic acids.
  • Another important accelerator is 1,4-diazabicyclo- (2.2.2) octane, abbreviated to DABCO.
  • Non-basic substances can also be used as accelerators.
  • Metal compounds may be mentioned here, for example iron acetylacetonate, tin (II) octoate, dibutyltin dilaurate and tin mercaptides.
  • the accelerators can be present in amounts of 0.001 to 1% by weight, based on the adhesive.
  • the two-component polyurethane adhesives according to the invention are usually stored in two-component form until they are used, that is until that point in time the polyol and isocyanate components are kept separately. For use, these two compounds are mixed together in a manner known per se and the mixture is applied to the substrates to be bonded.
  • the polyurethane adhesives according to the invention are suitable for connecting a large number of flexible and rigid substrates. In this way, plastics, wood and metals can be connected to one another in a variety of ways.
  • the adhesives according to the invention are particularly suitable for bonding wood to itself or other substrates. It is also possible to use the adhesives as a filler with adhesive properties, for example in the restoration of wooden objects.
  • Another use is conceivable as a potting or sealing compound.
  • Baylith L powder (Bayer AG) is a zeolite that is used as a drying agent.
  • Socal 312 N (Solvay) is chalk coated with stearic acid, which is used as a filler.
  • Formrez UL 24 (Witco) is an Sn-containing accelerator.
  • compositions of the adhesives are summarized in Table 1.
  • Sovermol ( R ) VP 95 (Henkel) is the reaction product of equimolar amounts of an epoxidized oleyl alcohol and ethylene glycol1.
  • the OH number (OHZ) was determined according to DIN 53240.
  • test specimens were produced in accordance with DIN 53254 with the adhesives from Table 1 and then based on EN (European Standard) 204 (previous edition DIN 68602 from April 1979) "Assessment of adhesives for non-loadbearing components for connecting Wood and wood-based materials "checked.
  • the adhesive bond is stored for 7 days in a normal climate 20/65 before measuring the tensile shear strength and then in water at 20 ° C. for 4 days.
  • a value> 2 N / mm2 is required to meet the standard.
  • the adhesive bond is stored for 7 days in a normal climate 20/65, 6 hours in boiling water and 2 hours in water at a temperature of 20 ° C before measuring the tensile shear strength.
  • a value> 4 N / mm ⁇ is required to meet the standard.
  • the Shore D hardness is determined according to DIN 53505. The results are summarized in Table 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The description relates to two-part polyurethane adhesives with improved adhesive power in damp conditions, containing oleochemical polyols as the polyol component. The adhesive power is improved by the addition of 2 to 7 wt.% in relation to the polyol of a diol or diol mixture or a trifunctional hydroxyl compound with hydroxyl numbers from 1100 to 1850.

Description

ZweiJkomponenten-Pol urethaiiklebstof £ mit verbessertem Two component pol urethai adhesive with improved
KlebevermögenAdhesive power
Gebiet der Erf ndungField of the Invention
Die Erfindung betrifft einen zweikomponentigen Polyurethanklebstoff mit verbesserten Klebeeigenschaften, der als Polyolkomponente Polyole auf Basis nachwachsender Roh¬ stoffe enthält.The invention relates to a two-component polyurethane adhesive with improved adhesive properties, which contains polyols based on renewable raw materials as the polyol component.
Stand der TechnikState of the art
Polyurethanklebstoffe sind seit Jahren bekannt und weit ver¬ breitet. Von besonderer Wichtigkeit, insbesondere bei tech¬ nischen Anwendungen, sind dabei die Zweikomponentenkleb¬ stoffe, die vom Verwender vor Verkleben zu einer Reaktions¬ mischung verrührt werden, die dann nach Auftragen auf die zu verklebenden Substrate aushärtet. Derartige Zweikomponenten- klebstoffe bestehen aus einer Polyolkomponente und einer Isocyanatkomponente der Funktionalität 2 und höher.Polyurethane adhesives have been known and widely used for years. Of particular importance, especially in technical applications, are the two-component adhesives which are mixed by the user prior to bonding to form a reaction mixture which then hardens after application to the substrates to be bonded. Such two-component adhesives consist of a polyol component and an isocyanate component with functionality 2 and higher.
Als Polyole auf Basis nachwachsender Rohstoffe eignen sich unter anderem Ricinusöl oder die in der DE-Al 33 47 045 be¬ schriebenen oleochemischen Polyole, die im wesentlichen durch Reaktion epoxidierter Fettstoffe mit Alkoholen zugänglich sind.Suitable polyols based on renewable raw materials include castor oil or the oleochemical polyols described in DE-Al 33 47 045, which essentially consist of Reaction of epoxidized fatty substances with alcohols are accessible.
Die Ringöffnung epoxidierter Fettsäureester mit Diolen und die Verwendung der resultierenden fettchemischen Polyole als Rohstoffe für Polyurethane wird in der CA-A 850 672 be¬ schrieben. In dieser Patentschrift wird ausgeführt, daß zur Erreichung einer ausreichenden Topfzeit der Polyurethane das nicht abreagierte Diol abdestilliert werden muß. In Bei¬ spiel 1 werden detaillierte Vorschriften zur Entfernung von Diolspuren durch eine Vakuum-Dampfdestillation gegeben.The ring opening of epoxidized fatty acid esters with diols and the use of the resulting oleochemical polyols as raw materials for polyurethanes is described in CA-A 850 672. In this patent it is stated that the unreacted diol must be distilled off in order to achieve a sufficient pot life for the polyurethanes. In example 1, detailed regulations for the removal of diol traces by vacuum steam distillation are given.
Die nach der Lehre der DE-Al 33 47 045 hergestellten Kleb¬ stoffe haben den Nachteil, daß sie unter Klimabedingungen mit hoher Luftfeuchtigkeit oder bei Belastung mit Schwitzwasser keine hohe Klebkraft besitzen. Nach der Lehre der DE-Al 40 41 119 sollte diesem Mangel dadurch abgeholfen wer¬ den, daß mehrfunktionelle, nicht-verseifbare Alkohole, die durch ringöffnende Umsetzung epoxidierter innenständiger Olefine oder epoxidierter Fettalkohole erhalten werden, al¬ lein oder in Abmischung mit niedermolekularen Diolen oder Triolen den Polyolen auf Basis nachwachsender Rohstoffe in Mengen von 3 bis 50 Gew.% bezogen auf entstehendes Polyurethan zugesetzt werden. Wie aus den dort angegebenen Beispielen ersichtlich, bedeutet das, daß bevorzugt 33 Gew.% bezogen auf das Polyol, im Minimalfall 11 Gew.% bezogen auf das Polyol eingesetzt werden.The adhesives produced according to the teaching of DE-Al 33 47 045 have the disadvantage that they do not have a high adhesive strength under climatic conditions with high atmospheric humidity or when exposed to condensation water. According to the teaching of DE-Al 40 41 119, this deficiency should be remedied by the fact that polyfunctional, non-saponifiable alcohols, which are obtained by ring-opening reaction of epoxidized internal olefins or epoxidized fatty alcohols, alone or in admixture with low molecular weight diols or Triplets can be added to the polyols based on renewable raw materials in amounts of 3 to 50% by weight based on the polyurethane formed. As can be seen from the examples given there, this means that preferably 33% by weight based on the polyol, in a minimal case 11% by weight based on the polyol, are used.
Die genannten Alkohole sind aber nur durch aufwendige Ver¬ fahren herzustellen, z.B. muß zunächst ein ungesättigter Fettalkohol epoxidiert und danach einer Ringöffnung unter¬ zogen werden.However, the alcohols mentioned can only be prepared by complex processes, for example an unsaturated one first Epoxidized fatty alcohol and then subjected to a ring opening.
Die Ringöffnung von Epoxiden mit mehrwertigen Alkoholen er¬ fordert wegen der Vernetzungsgefahr bei der Reaktion eine sorgfältige Kontrolle.The ring opening of epoxides with polyhydric alcohols requires careful control because of the risk of crosslinking during the reaction.
Es hat sich gezeigt, daß die Steigerung des Klebevermögens, insbesondere unter Feuchtebedingungen, durch Zusatz von Diolen oder Diolgemischen und/oder trifunktionellen Hydro¬ xylVerbindungen kein additiver Effekt ist, der sich bei weiterer Erhöhung der Mengen beliebig steigern ließe. Viel¬ mehr liegt bezüglich der Menge ein Optimum vor.It has been shown that the increase in the adhesive capacity, in particular under moist conditions, by adding diols or diol mixtures and / or trifunctional hydroxyl compounds is not an additive effect which could be increased as desired if the amounts were increased further. Rather, there is an optimum in terms of quantity.
Weiterhin hat sich gezeigt, daß nicht alle Diole oder trifunktionellen Hydroxy1Verbindungen, sondern nur solche mit bestimmten Hydroxylzahlen oder Gemische mit diesen Hydroxyl¬ zahlen geeignet sind.Furthermore, it has been shown that not all diols or trifunctional hydroxyl compounds, but only those with certain hydroxyl numbers or mixtures with these hydroxyl numbers are suitable.
Die Aufgabe der Erfindung bestand dementsprechend darin, durch Zusatz von Diolen oder Diolgemischen und/oder trifunk¬ tionellen HydroxylVerbindungen oder Mischungen daraus mit bestimmten Hydroxylzahlen in bestimmten Mengen zur Polyol¬ komponente eine einfach durchzuführende Methode zur Verfü¬ gung zu stellen, mit der die Klebkraft von oleochemische Polyole enthaltenden Zweikomponentenpolyurethan-Klebstoffen, vor allem unter Feuchtebedingungen, verbessert werden kann. Beschreibung der ErfindungAccordingly, the object of the invention was to provide an easy-to-carry out method by adding diols or diol mixtures and / or trifunctional hydroxyl compounds or mixtures thereof with certain hydroxyl numbers in certain amounts to the polyol component, with which the adhesive strength of Two-component polyurethane adhesives containing oleochemical polyols, especially under moist conditions, can be improved. Description of the invention
Gegenstand der Erfindung sind Zweikomponenten- Polyurethanklebstoffe, auf Basis a) einer Polyolkomponente, enthaltend oleochemische Polyole, und b) einer Isocyanatkomponente, bei denen die Komponente a) 2 bis 7 Gew.% difunktioneller und/oder trifunktioneller Alkohole oder deren Gemische - be¬ zogen auf das oleochemische Polyol - enthält und daß die Hy- droxylzahl der Alkohole oder deren Gemische 1100 bis 1850 beträgt.The invention relates to two-component polyurethane adhesives based on a) a polyol component containing oleochemical polyols, and b) an isocyanate component in which component a) comprises 2 to 7% by weight of difunctional and / or trifunctional alcohols or mixtures thereof on the oleochemical polyol - and that the hydroxyl number of the alcohols or their mixtures is 1100 to 1850.
Ein weiterer Gegenstand der Erfindung ist eine oleochemische Polyole enthaltende Polyolkomponente zur Herstellung von Polyurethanen, in der zusätzlich 2 bis 7 Gew.% difunktioneller und/oder trifunktioneller Alkohole oder deren Gemische mit Hydroxylzahlen zwischen 1100 bis 1850 - bezogen auf das oleochemische Polyol - enthalten sind.Another object of the invention is an oleochemical polyol-containing polyol component for the production of polyurethanes, which additionally contains 2 to 7% by weight of difunctional and / or trifunctional alcohols or their mixtures with hydroxyl numbers between 1100 and 1850, based on the oleochemical polyol.
Ein weiterer Gegenstand der Erfindung betrifft die Verwendung von Zweikomponenten-Polyurethanklebstoffen zum Verkleben von starren oder flexiblen Substraten, insbesondere von Kunst¬ stoffen, Metallen, Glas oder besonders bevorzugt Holz mit¬ einander oder mit sich selbst.Another object of the invention relates to the use of two-component polyurethane adhesives for bonding rigid or flexible substrates, in particular plastics, metals, glass or, particularly preferably, wood to one another or to one another.
Als Diole oder Diolgemische können Diole mit Hydroxylzahlen von 1100 bis 1500, bevorzugt 1150 bis 1350, besonders bevor¬ zugt 1200 bis 1300 eingesetzt werden, z.B. 1,2-Propandiol, 1,3-Propandiol, 2,3-Butandiol oder 1,4-Butendiol. Besonders bevorzugt wird 1,4-Butandiol eingesetzt.Diols or diol mixtures which can be used are diols having hydroxyl numbers from 1100 to 1500, preferably 1150 to 1350, particularly preferably 1200 to 1300, for example 1,2-propanediol, 1,3-propanediol, 2,3-butanediol or 1,4-butenediol. 1,4-Butanediol is particularly preferably used.
Im Sinne der Erfindung können auch Diolgemische mit Hydro¬ xylzahlen von 1100 bis 1500, bevorzugt 1150 bis 1350, beson¬ ders bevorzugt 1200 bis 1300 eingesetzt werden. Dabei ist es nicht erforderlich, daß die Bestandteile des Gemisches je¬ weils Hydroxylzahlen im genannten Bereich aufwiesen, vielmehr ist auch der Einsatz eines Gemisches aus Diolen möglich, die einzeln Hydroxylzahlen unterhalb 1100 oder oberhalb 1500 be¬ sitzen, z.B. von Gemischen aus 1,2-Ethandiol und 1,6-Hexan- diol, die in den Hydroxylzahlenbereich von 1100 bis 1500 fallen.According to the invention, diol mixtures with hydroxyl numbers from 1100 to 1500, preferably 1150 to 1350, particularly preferably 1200 to 1300 can also be used. It is not necessary for the constituents of the mixture to have hydroxyl numbers in the range mentioned, rather it is also possible to use a mixture of diols which individually have hydroxyl numbers below 1100 or above 1500, e.g. of mixtures of 1,2-ethanediol and 1,6-hexanediol which fall in the hydroxyl number range from 1100 to 1500.
Weiterhin können trifunktionelle Hydroxylverbindungen mit Hydroxylzahlen von 1100 bis 1850 eingesetzt werden, z.B. Trimethylolpropan, Trimethylolethan oder das Additionsprodukt von 1 mol Ethylenoxid an Glycerin. Besonders bevorzugt wird Glycerin eingesetzt.Furthermore, trifunctional hydroxyl compounds with hydroxyl numbers from 1100 to 1850 can be used, e.g. Trimethylolpropane, trimethylolethane or the addition product of 1 mol ethylene oxide with glycerol. Glycerin is particularly preferably used.
Im Sinne der Erfindung können auch Gemische trifunktioneller Verbindungen, deren Hydroxylzahlen im Bereich zwischen 1100 und 1850 liegen, verwendet werden. Die Hydroxylzahlen der Einzelkomponenten müssen wie bei den Diolgemischen nicht in diesem Bereich liegen.Mixtures of trifunctional compounds whose hydroxyl numbers are in the range between 1100 and 1850 can also be used for the purposes of the invention. As with the diol mixtures, the hydroxyl numbers of the individual components need not be in this range.
Die Mengen der Diole oder Diolgemische und/oder der trifunk¬ tionellen Hydroxylverbindungen oder ihrer Mischungen liegen zwischen 2 und 7 Gew.%, bevorzugt zwischen 4 und 6 Gew.% be¬ zogen auf das Polyol. Die Polyole der erfindungsgemäßen Polyurethanklebstoffe kön¬ nen oleochemische Polyole sein. Unter oleochemischen Polyolen versteht man Polyole auf Basis natürlicher öle und Fette, z.B. die Reaktionsprodukte von epoxidierten Fettstoffen mit mono-, di- oder polyfunktionellen Alkoholen oder Glycerinester langkettiger Fettsäuren, die zumindest teil¬ weise mit Hydroxylgruppen substituiert sind.The amounts of the diols or diol mixtures and / or the trifunctional hydroxyl compounds or their mixtures are between 2 and 7% by weight, preferably between 4 and 6% by weight, based on the polyol. The polyols of the polyurethane adhesives according to the invention can be oleochemical polyols. Oleochemical polyols are understood to mean polyols based on natural oils and fats, for example the reaction products of epoxidized fatty substances with mono-, di- or polyfunctional alcohols or glycerol esters of long-chain fatty acids which are at least partially substituted with hydroxyl groups.
Eine Untergruppe dieser Verbindungen sind die Ringöffnungs¬ produkte epoxidierter Triglyceride, also epoxidierter Fettsäureglycerinester, bei denen die Ringöffnung unter Er¬ halt der Esterbindungen ausgeführt worden ist. Zur Herstel¬ lung der Ringöffnungsprodukte kann man von einer Vielzahl epoxidierter Triglyceride pflanzlichen oder tierischen Ur¬ sprungs ausgehen. So sind beispielsweise epoxidierte Triglyceride geeignet, die 2 bis 10 Gewichtsprozent Epoxidsauerstoff aufweisen. Derartige Produkte sind durch Epoxidation der Doppelbindungen aus einer Reihe von Fetten und Ölen herstellbar, z.B. Rindertalg, Palmöl, Erdnußöl, Rüböl, Baumwollsaatöl, Sojaöl, Sonnenblumenöl und Leinöl. Besonders bevorzugte epoxidierte Triglyceride sind epoxidiertes Sojaöl und epoxidiertes Leinöl.A subgroup of these compounds are the ring opening products of epoxidized triglycerides, ie epoxidized fatty acid glycerol esters, in which the ring opening has been carried out while maintaining the ester bonds. A large number of epoxidized triglycerides of vegetable or animal origin can be used to produce the ring opening products. For example, epoxidized triglycerides are suitable which have 2 to 10 percent by weight of epoxy oxygen. Such products can be made by epoxidation of the double bonds from a range of fats and oils, e.g. Beef tallow, palm oil, peanut oil, turnip oil, cottonseed oil, soybean oil, sunflower oil and linseed oil. Particularly preferred epoxidized triglycerides are epoxidized soybean oil and epoxidized linseed oil.
Als Alkohole für die Ringöffnung der epoxidierten Triglyceride können Methanol, Ethanol, Propanol, Isopropanol, Butanol, Hexanol, 2-Ethylhexanol, Fettalkohole mit 6 bis 22 C-Atomen, Cyclohexanol, Benzylalkohol, 1,2-Ethandiol, 1,2- Propandiol, 1,3-Propandiol, 1,4-Butandiol, 1,6-Hexandiol, Neopentylglykol, Trimethylolpropan, Glycerin, Trimethylol- ethan, Pentaerythrit, Sorbit sowie ethergruppenhaltige Hydroxyverbindungen wie Alkylglykole oder oligomere Glykole sowie oligomere Glycerine eingesetzt werden.As alcohols for the ring opening of the epoxidized triglycerides, methanol, ethanol, propanol, isopropanol, butanol, hexanol, 2-ethylhexanol, fatty alcohols with 6 to 22 carbon atoms, cyclohexanol, benzyl alcohol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentylglycol, trimethylolpropane, glycerol, trimethylolethane, pentaerythritol, sorbitol and those containing ether groups Hydroxy compounds such as alkyl glycols or oligomeric glycols and oligomeric glycerols can be used.
Die Ringöffnungsreaktion epoxidierter Fettsäureester oder Triglyceride mit einem Alkohol kann gegebenenfalls von einer Umesterung mit sich selber oder anderen, nachträglich zuge¬ fügten Triglyceriden, wie zum Beispiel Palmöl, Erdnußöl, Rüböl, Baumwollsaatöl, Sojaöl, Sonnenblumenöl und Leinöl, gefolgt sein. Solche oleochemischen Polyole sind z.B. in der deutschen Patentanmeldung DE-Al 41 28 649 beschrieben.The ring-opening reaction of epoxidized fatty acid esters or triglycerides with an alcohol can optionally be followed by a transesterification with itself or other subsequently added triglycerides, such as palm oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, sunflower oil and linseed oil. Such oleochemical polyols are e.g. described in German patent application DE-Al 41 28 649.
Eine weitere Gruppe der oleochemischen Polyole sind Ringöff- nungs- und Umesterungsprodukte von epoxidierten Fettsäure¬ estern niederer Alkohole, also von epoxidierten Fettsäureme¬ thyl-, -ethyl-, -propyl- oder -butylestern. Bevorzugt sind hier die Ringöffnungs- oder Umesterungsprodukte mit Alkoholen der Funktionalität 2 bis 4, insbesondere die Umsetzungspro¬ dukte mit Ethylenglykol, Propylenglyko1, oligomeren Ethylenglykolen, oligomeren Propylenglykolen, Glycerin, Trimethylolpropan oder Pentaerythrit. Die Herstellung derar¬ tiger Produkte kann nach bekannten Epoxidations- oder Ring¬ öffnungsverfahren erfolgen, wobei die Umesterung während oder nach dem Ringöffnungsschritt durch Entfernen des niederen Alkohols aus den Reaktionsgleichgewicht durchgeführt werden kann. Bevorzugt sind Ringöffnungs- und Umesterungsprodukte, bei denen ein molares Verhältnis zwischen epoxidiertem Fett¬ säureester und dem zur Umsetzung verwendeten Alkohol von 1:1 bis 1:10 angewandt worden ist.Another group of oleochemical polyols are ring opening and transesterification products of epoxidized fatty acid esters of lower alcohols, ie of epoxidized fatty acid methyl, ethyl, propyl or butyl esters. The ring opening or transesterification products with alcohols of functionality 2 to 4 are preferred here, in particular the reaction products with ethylene glycol, propylene glycol 1, oligomeric ethylene glycols, oligomeric propylene glycols, glycerol, trimethylolpropane or pentaerythritol. Such products can be produced by known epoxidation or ring-opening processes, and the transesterification can be carried out during or after the ring-opening step by removing the lower alcohol from the reaction equilibrium. Ring opening and transesterification products are preferred, in which a molar ratio between epoxidized fatty acid ester and the alcohol used for the reaction of 1: 1 to 1:10 has been used.
Ebenfalls zu den oleochemischen Polyolen zählen die Umset¬ zungsprodukte epoxidierter Fettalkohole mit C2-C8-Alkoholen der Funktionalität 1 bis 10, insbesondere 2 bis 4, im molaren Verhältnis der Epoxidgruppen zu den Hydroxylgruppen von 1:1 bis 1:10.The oleochemical polyols also include the reaction products of epoxidized fatty alcohols with C2-C8 alcohols functionality 1 to 10, in particular 2 to 4, in the molar ratio of the epoxy groups to the hydroxyl groups from 1: 1 to 1:10.
Im Rahmen der Erfindung ist auch die Verwendung von oleochemischen Polyolen möglich, die über die Umesterung von di- oder polyfunktionellen Alkoholen wie z.B. dem Additions¬ produkt von Ethylenoxid oder Propylenoxid an Glycerin mit Triglyceriden, wie z.B. Palmöl, Erdnußöl, Rüböl, Baumwoll- saatöl, Sojaöl, Sonnenblumenöl und Leinöl, zugänglich sind.Within the scope of the invention it is also possible to use oleochemical polyols which are obtained via the transesterification of di- or polyfunctional alcohols, e.g. the addition product of ethylene oxide or propylene oxide to glycerol with triglycerides, e.g. Palm oil, peanut oil, turnip oil, cottonseed oil, soybean oil, sunflower oil and linseed oil are accessible.
Ebenso können Polyole verwendet werden, die nach der Lehre der DE-Al 41 24 665 durch die Umesterung von polymerisiertem Glycerin mit den vorstehend genannten Triglyceriden erhält¬ lich sind.It is also possible to use polyols which, according to the teaching of DE-A1 41 24 665, can be obtained by transesterifying polymerized glycerol with the abovementioned triglycerides.
Die Polyole können Hydroxylzahlen von 50 bis 400, bevorzugt 100 bis 300 aufweisen.The polyols can have hydroxyl numbers from 50 to 400, preferably 100 to 300.
Besonders bevorzugt ist die Verwendung von Ricinusöl als oleochemisches Polyol.The use of castor oil as an oleochemical polyol is particularly preferred.
Die zweite Komponente der erfindungsgemäßen Klebstoffe, die sogenannte Isocyanatkomponente, kann eine Isocyanatverbindung mit der Funktionalität von 2 bis 4 enthalten.The second component of the adhesives according to the invention, the so-called isocyanate component, can contain an isocyanate compound with the functionality of 2 to 4.
Geeignet sind sowohl aromatische als auch aliphatische, monocyclische wie polycylische, mehrfunktionelle Isocyanat- verbindungen. Als aromatische di- oder höherfunktionelle Isocyanate eignen sich 2,4-Toluylendiisocyanat, 2,6- Toluylendiisocyanat oder seine Mischungen, Diphenylmethan- diisocyanat oder seine technischen Qualitäten, die höher- funktionelle Isocyanate enthalten. Bevorzugt werden alipha- tische Isocyanate der Funktionaltät 2 und höher eingesetzt, z.B. Isophorondiisocyanat, trimerisiertes, Isocyanuratgruppen enthaltendes Isophorondiisocyanat oder 1,6-Hexandiisocyanat, trimerisiertes, Biuret-Gruppen enthaltendes 1,6-Hexandiiso- cyanat und Dicyclohexylmethandiisocyanat.Both aromatic and aliphatic, monocyclic and polycyclic, multifunctional isocyanate compounds are suitable. Suitable aromatic di- or higher-functional isocyanates are 2,4-tolylene diisocyanate, 2,6- Toluene diisocyanate or its mixtures, diphenylmethane diisocyanate or its technical qualities that contain higher-functional isocyanates. Aliphatic isocyanates of functionality 2 and higher are preferably used, for example isophorone diisocyanate, trimerized isophorone diisocyanate or isocyanurate groups or 1,6-hexane diisocyanate, trimerized 1,6-hexane diisocyanate containing biuret groups and dicyclohexylmethane diisocyanate.
Nach einer besonders bevorzugten Ausführungsform der Erfin¬ dung wird als aliphatische Isocyanatverbindung ein modifi¬ ziertes, trimerisiertes 1,6-Hexandiisocyant eingesetzt, das unter der Bezeichnung "Desmodur(R) DA" (Bayer AG, Leverkusen, FRG) im Handel ist.According to a particularly preferred embodiment of the invention, a modified, trimerized 1,6-hexanediisocyanate is used as the aliphatic isocyanate compound, which is commercially available under the name "Desmodur ( R ) DA" (Bayer AG, Leverkusen, FRG).
Weiterhin können in den erfindungsgemäßen Zweikomponenten- Polyurethanklebstoffen als Isocyanate auch Addukte mehrfunk- tioneller Isocyanate an mehrfunktionelle Alkohole, etwa die Umsetzungsprodukte eines der vorgenannten aromatischen oder aliphatischen Diisocyanate mit beispielsweise Ethylenglykol, Propylenglykol, Glycerin, Trimethylolpropan oder Pentaery- thrit eingesetzt werden.Furthermore, adducts of polyfunctional isocyanates with polyfunctional alcohols, such as the reaction products of one of the aforementioned aromatic or aliphatic diisocyanates with, for example, ethylene glycol, propylene glycol, glycerol, trimethylolpropane or pentaerythritol, can also be used as isocyanates in the two-component polyurethane adhesives according to the invention.
Auch die Umsetzungsprodukte von Diisocyanaten mit Polyetherpolyolen, z.B. Polyetherpolyolen auf Basis von Polypropylenoxid, können als Isocyanatkomponente verwendet werden.The reaction products of diisocyanates with polyether polyols, e.g. Polyether polyols based on polypropylene oxide can be used as the isocyanate component.
Das Verhältnis der in der Isocyanatkomponente enthaltenen Isocyanatgruppen zu den in der Polyolkomponente enthaltenen OH-Gruppen liegt in der Regel im Bereich der Äquivalenz, d. h. das Verhältnis NCO:OH liegt zwischen 1,1 und 0,9, be¬ vorzugt um 1,0.The ratio of the isocyanate groups contained in the isocyanate component to the OH groups contained in the polyol component is generally in the range of equivalence, ie the NCO: OH ratio is between 1.1 and 0.9, preferably around 1.0.
Die erfindungsgemäßen Zweikomponenten-Polyurethanklebstoffe können weiterhin verschiedene Hilfsstoffe enthalten, die vorzugsweise der Polyolkomponente zugemischt werden. Einge¬ setzt werden können hier z.B. Füllstoffe. Als Füllstoffe ge¬ eignet sind gegenüber Isocyanaten nicht reaktive anorganische Verbindungen wie Kreide, durch eine Beschichtung vorbehan¬ delte Kreide, Kalkmehl, gefällte Kieselsäuren, Zeolithe, Bentonite, Glashohlkugeln, gemahlene Mineralien sowie andere, dem auf dem Arbeitsgebiet tätigen Fachmann bekannte anorga¬ nische Füllstoffe. Witerhin können auch organische Füllstoffe verwendet werden, insbesondere Faserkurzschnitte, Kunst¬ stoffhohlkugeln und anderes. Bevorzugt sind Füllstoffe, die den Klebstoffmischungen Thixotropie verleihen.The two-component polyurethane adhesives according to the invention can furthermore contain various auxiliaries, which are preferably added to the polyol component. Can be used here e.g. Fillers. Suitable fillers are inorganic compounds which are not reactive towards isocyanates, such as chalk, chalk treated by a coating, chalk powder, precipitated silicas, zeolites, bentonites, hollow glass spheres, ground minerals and other inorganic fillers known to the person skilled in the art . Furthermore, organic fillers can also be used, in particular fiber short cuts, hollow plastic spheres and others. Fillers are preferred which impart thixotropy to the adhesive mixtures.
Außer den genannten Verbindungen können die erfindungsgemäßen Polyurethanklebstoffe noch weitere Hilfsstoffe enthalten. Zu erwähnen sind Weichmacher, Flammschutzmittel, Verzögerer, Farbstoffe und Alterungsschutzmittel wie sie in entsprechen¬ den Klebstoffen bekannt sind. Verwendet werden können, ob¬ gleich nicht bevorzugt, auch Lösungsmittel, die nicht mit den Isocyanatgruppen reagieren, wie Ester, Ketone und aromatische Kohlenwasserstoffe.In addition to the compounds mentioned, the polyurethane adhesives according to the invention may also contain other auxiliaries. Plasticizers, flame retardants, retarders, dyes and anti-aging agents such as are known in corresponding adhesives are to be mentioned. Solvents which do not react with the isocyanate groups, such as esters, ketones and aromatic hydrocarbons, can also be used, although not preferred.
Die Hilfsstoffe können in Mengen von 0,1 bis 75 Gew.% bezogen auf den Klebstoff enthalten sein.The auxiliaries can be contained in amounts of 0.1 to 75% by weight, based on the adhesive.
Die erfindungsgemäßen Klebstoffe können weiterhin Beschleu¬ niger enthalten. Geeignet sind z.B. tertiäre Basen, wie Bis-( ,N-dimethylamino)-diethylether, N,N-Dimethylbenzylamin, N-Methylmorpholin sowie die Umsetzungsprodukte von Dialkyl-(ß-hydroxyethyl)-aminen mit Monoisocyanaten und Veresterungsprodukte dieser Amine mit Dicarbonsäuren. Ein weiterer wichtiger Beschleuniger ist 1,4-Diazabicyclo- (2.2.2)-octan, abgekürzt DABCO.The adhesives according to the invention can furthermore contain accelerators. Suitable are, for example, tertiary bases such as Bis- (, N-dimethylamino) diethyl ether, N, N-dimethylbenzylamine, N-methylmorpholine and the reaction products of dialkyl- (β-hydroxyethyl) amines with monoisocyanates and esterification products of these amines with dicarboxylic acids. Another important accelerator is 1,4-diazabicyclo- (2.2.2) octane, abbreviated to DABCO.
Ferner können nicht-basische Substanzen als Beschleuniger verwendet werden. Hier seien MetallVerbindungen genannt, beispielsweise Eisenacetylacetonat, Zinn-(II)-octoat, Dibutylzinndilaurat und Zinnmercaptide.Non-basic substances can also be used as accelerators. Metal compounds may be mentioned here, for example iron acetylacetonate, tin (II) octoate, dibutyltin dilaurate and tin mercaptides.
Die Beschleuniger können in Mengen von 0,001 bis 1 Gew.% be¬ zogen auf den Klebstoff enthalten sein.The accelerators can be present in amounts of 0.001 to 1% by weight, based on the adhesive.
Die erfindungsgemäßen Zweikomponenten-Polyurethanklebstoffe werden üblicherweise bis zu ihrer Anwendung zweikomponentig gelagert, das heißt bis zu diesem Zeitpunkt werden Polyol- und Isocyanatkomponente getrennt aufbewahrt. Zur Anwendung werden diese beiden Verbindungen in an sich bekannter Weise miteinander vermischt und das Gemisch auf die zu verklebenden Substrate aufgetragen.The two-component polyurethane adhesives according to the invention are usually stored in two-component form until they are used, that is until that point in time the polyol and isocyanate components are kept separately. For use, these two compounds are mixed together in a manner known per se and the mixture is applied to the substrates to be bonded.
Die erfindungsgemäßen Polyurethanklebstoffe sind zum Verbin¬ den einer Vielzahl flexibler und starrer Substrate geeignet. So können Kunststoffe, Holz und Metalle in vielfältiger Weise unter sich oder miteinander verbunden werden. Besonders geeignet sind die erfindungsgemäßen Klebstoffe zur Verklebung von Holz mit sich selber oder anderen Substraten. Ebenso ist eine Verwendung der Klebstoffe als Spachtelmasse mit klebenden Eigenschaften, zum Beispiel bei der Restaurie¬ rung von Holzgegenständen, möglich.The polyurethane adhesives according to the invention are suitable for connecting a large number of flexible and rigid substrates. In this way, plastics, wood and metals can be connected to one another in a variety of ways. The adhesives according to the invention are particularly suitable for bonding wood to itself or other substrates. It is also possible to use the adhesives as a filler with adhesive properties, for example in the restoration of wooden objects.
Eine weitere Verwendung ist als Verguß- oder Dichtmasse denkbar. Another use is conceivable as a potting or sealing compound.
BeispieleExamples
Alle prozentualen Angaben in den Beispielen verstehen sich, sofern nicht anders angeben, als Gewichtsprozent.Unless stated otherwise, all percentages in the examples are percentages by weight.
Die Untersuchungen wurden an folgender 2K-Polyurethan- Klebstoffrezeptur durchgeführt:The investigations were carried out on the following two-component polyurethane adhesive formulation:
Polyol-Komponente:Polyol component:
Ricinusöl (Hydroxyl-Zahl = 165) 42,0 gCastor oil (hydroxyl number = 165) 42.0 g
Baylith(R) L-Pulver 8,0 gBaylith ( R ) L powder 8.0 g
Socal(R) 312 N 49,9 gSocal ( R ) 312 N 49.9 g
Formrez(R) UL-24 0,1 gFormrez ( R ) UL-24 0.1 g
Polyol-Komponente 100,0 gPolyol component 100.0 g
Baylith L-Pulver (Firma Bayer AG) ist ein Zeolith, der als Trockenmittel eingesetzt wird.Baylith L powder (Bayer AG) is a zeolite that is used as a drying agent.
Socal 312 N (Firma Solvay) ist mit Stearinsäure beschichtete Kreide, die als Füllstoff eingesetzt wird.Socal 312 N (Solvay) is chalk coated with stearic acid, which is used as a filler.
Formrez UL 24 (Firma Witco) ist ein Sn-haltiger Beschleuni¬ ger.Formrez UL 24 (Witco) is an Sn-containing accelerator.
Zu jeweils 100 g der Härterkomponente (entsprechend 0,124 mol OH) wurden jeweils äquivalente molare Mengen an Diolen oder Triolen gegeben (0,044 mol) und mit dem modifizierten Polyisocyanat Desmodur(R) DA der Firma Bayer (NCO-Gehalt = 19,5%) vermischt. Das NCO:OH-Verhältnis betrug 1:1.Equivalent molar amounts of diols were added to 100 g of the hardener component (corresponding to 0.124 mol OH) or triplets (0.044 mol) and mixed with the modified polyisocyanate Desmodur (R) DA from Bayer (NCO content = 19.5%). The NCO: OH ratio was 1: 1.
Die Zusammensetzungen der Klebstoffe sind in Tabelle 1 zu¬ sammengef ßt.The compositions of the adhesives are summarized in Table 1.
Tabelle 1: Klebstoff-ZusammensetzungTable 1: Adhesive composition
Bei- Di-/Triol OHZ Menge Desmodur DA spiel [g] [g]Example- Di- / Triol OHZ amount Desmodur DA game [g] [g]
1 1,4-Butandiol 1247 2,00 36,21 1,4-butanediol 1247 2.00 36.2
2 1,2-Propandiol 1476 1,69 36,22 1,2-propanediol 1476 1.69 36.2
3 Glycerin 1829 1,36 36,23 glycerin 1829 1.36 36.2
VI 1,2-Ethandiol 1810 1,38 36,2VI 1,2-ethanediol 1810 1.38 36.2
V2 1,5-Pentandiol 1079 2,31 36,2V2 1,5-pentanediol 1079 2.31 36.2
V3 Diethylenglykol 1058 2,36 36,2V3 diethylene glycol 1058 2.36 36.2
V4 Sovermol VP 95 400 6,23 36,2V4 Sovermol VP 95 400 6.23 36.2
V5 1,4-Butandiol 1247 1,00 31,4V5 1,4-butanediol 1247 1.00 31.4
V6 1,4-Butandiol 1247 4,00 45,8V6 1,4-butanediol 1247 4.00 45.8
V7 ohne - - 26,6 Legende zu Tabelle 1:V7 without - - 26.6 Legend for table 1:
Sovermol(R) VP 95 (Henkel) ist das Reaktionsprodukt aus äquimolaren Mengen eines epoxidierten Oleylalkohols und Ethylenglyko1.Sovermol ( R ) VP 95 (Henkel) is the reaction product of equimolar amounts of an epoxidized oleyl alcohol and ethylene glycol1.
Die OH-Zahl (OHZ) wurde nach DIN 53240 bestimmt.The OH number (OHZ) was determined according to DIN 53240.
Für die anwendungstechnische Prüfung der Klebstoffe wurden Prüfkörper nach DIN 53254 mit den Klebstoffen aus der Tabelle 1 hergestellt und anschließend in Anlehnung an die EN (Europäische Norm) 204 (frühere Ausgabe DIN 68602 von April 1979) "Beurteilung von Klebstoffen für nichttragende Bauteile zur Verbindung von Holz und Holzwerkstoffen" ge¬ prüft.For the application-related testing of the adhesives, test specimens were produced in accordance with DIN 53254 with the adhesives from Table 1 and then based on EN (European Standard) 204 (previous edition DIN 68602 from April 1979) "Assessment of adhesives for non-loadbearing components for connecting Wood and wood-based materials "checked.
Für die D3-Beanspruchungsgruppe (Lagerungsfolge 3) dieser Norm wird die Klebeverbindung vor der Messung der Zugscher¬ festigkeit 7 Tage bei Normalklima 20/65 und anschließend 4 Tage in Wasser von 20 °C gelagert. Zur Erfüllung der Norm wird ein Wert > 2 N/mm2 gefordert.For the D3 stress group (bearing sequence 3) of this standard, the adhesive bond is stored for 7 days in a normal climate 20/65 before measuring the tensile shear strength and then in water at 20 ° C. for 4 days. A value> 2 N / mm2 is required to meet the standard.
Für die D4-Beanspruchungsgruppe (Lagerungsfolge 5) wird die Klebeverbindung vor der Messung der Zugscherfestigkeit 7 Tage bei Normalklima 20/65, 6 Stunden in kochendem Wasser und 2 Stunden in Wasser mit einer Temperatur von 20 °C gelagert. Zur Erfüllung der Norm wird ein Wert > 4 N/mm^ gefordert.For the D4 stress group (bearing sequence 5), the adhesive bond is stored for 7 days in a normal climate 20/65, 6 hours in boiling water and 2 hours in water at a temperature of 20 ° C before measuring the tensile shear strength. A value> 4 N / mm ^ is required to meet the standard.
Die Shore D Härte wird nach DIN 53505 bestimmt. Die Ergebnisse sind in Tabelle 2 zusammengefaßt.The Shore D hardness is determined according to DIN 53505. The results are summarized in Table 2.
Tabelle 2 : Ergebnisse der anwendungstechnischen PrüfungTable 2: Results of the application test
Bsp. 1 2 3 VI V2Ex. 1 2 3 VI V2
D3-Prüfung 3,6 3,9 2,7 2,6 3,1D3 test 3.6 3.9 2.7 2.6 3.1
[N/mm2][N / mm 2 ]
D4-Prüfung 4,5 3,8 3,6 2,8 2,8D4 test 4.5 3.8 3.6 2.8 2.8
[N/mm2][N / mm 2 ]
Shore-Härte D 50 49 52 51 50Shore hardness D 50 49 52 51 50
Fortsetzung Tabelle 2Continuation of table 2
Bsp. V3 V4 V5 V6 V7E.g. V3 V4 V5 V6 V7
D3-Prüfung 2,8 3,5 3,2 3,4 3,1D3 test 2.8 3.5 3.2 3.4 3.1
[N/mm2][N / mm 2 ]
D4-Prüfung 2,2 3,9 3,7 2,4 3,0D4 test 2.2 3.9 3.7 2.4 3.0
[N/mm2][N / mm 2 ]
Shore-Härte D 48 50 49 52 47 Nur das erfindungsgemäße Beispiel 1 erfüllt die D3- und D4-Beanspruchungsgruppe der Europäischen Norm EN 204.Shore hardness D 48 50 49 52 47 Only example 1 according to the invention fulfills the D3 and D4 stress group of the European standard EN 204.
Die erfindungsgemäßen Beispiele 2 und 3 zeigen deutliche Verbesserungen des D4-Wertes. Examples 2 and 3 according to the invention show clear improvements in the D4 value.

Claims

Patentansprüche claims
1. Zweikomponenten-Polyurethanklebstoffe, auf Basis a) einer Polyolkomponente, enthaltend oleochemische Polyole, und b) einer Isocyanatkomponente, dadurch gekennzeichnet, daß die Komponente a) 2 bis 7 Gew.% difunktioneller und/oder trifunktioneller Alkohole oder deren Gemische - bezogen auf das oleochemische Polyol - enthält und daß die Hydroxylzahl der Alkohole oder deren Gemische 1100 bis 1850 beträgt.1. Two-component polyurethane adhesives, based on a) a polyol component containing oleochemical polyols, and b) an isocyanate component, characterized in that component a) 2 to 7 wt.% Difunctional and / or trifunctional alcohols or mixtures thereof - based on the oleochemical polyol - contains and that the hydroxyl number of the alcohols or their mixtures is 1100 to 1850.
2. Zweikomponenten-Polyurethanklebstoffe nach Anspruch 1, dadurch gekennzeichnet, daß die Komponente a) zusätzlich Diole oder Diolgemische mit einer Hydroxyl-Zahl zwischen 1150 und 1350 in Mengen von 2 bis 7 Gew.% bezogen auf das oleochemische Polyol enthält.2. Two-component polyurethane adhesives according to claim 1, characterized in that component a) additionally contains diols or diol mixtures with a hydroxyl number between 1150 and 1350 in amounts of 2 to 7% by weight, based on the oleochemical polyol.
3. Zweikomponenten-Polyurethanklebstoffe nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß die oleochemischen Polyole Ringöffnungsprodukte von epoxidierten Triglyceriden oder Fettsäureestern mit mono-, di- oder polyfunktionellen Alkoholen, wobei der Ringöffnungsreaktion gegebenenfalls eine Umesterungs- reaktion mit sich selber oder weiteren Triglyceriden folgt, darstellen.3. Two-component polyurethane adhesives according to claims 1 and 2, characterized in that the oleochemical polyols ring opening products of epoxidized triglycerides or fatty acid esters with mono-, di- or polyfunctional alcohols, the ring opening reaction optionally being followed by a transesterification reaction with itself or other triglycerides , represent.
4. Zweikomponenten-Polyurethanklebstoffe nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß das oleochemische Polyol Ricinusöl darstellt. 4. Two-component polyurethane adhesives according to claims 1 to 3, characterized in that the oleochemical polyol is castor oil.
5. Zweikomponenten-Polyurethanklebstoffe nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß die Isocyanatkomponente aliphatische Isocyanatverbindungen mit der Funktionaltät 2 bis 4 darstellt.5. Two-component polyurethane adhesives according to claims 1 to 4, characterized in that the isocyanate component is aliphatic isocyanate compounds with the functionality 2 to 4.
6. Zweikomponenten-Polyurethanklebstoffe nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß das molare Verhältnis der NCO-Gruppen aus der Isocyanatkomponente zu den OH-Gruppen aus der Polyolkomponente NCO:OH zwischen 1,1 und 0,9 liegt.6. Two-component polyurethane adhesives according to claims 1 to 5, characterized in that the molar ratio of the NCO groups from the isocyanate component to the OH groups from the polyol component NCO: OH is between 1.1 and 0.9.
7. Zweikomponenten-Polyurethanklebstoffe nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, daß Diole oder Diolgemische mit einer Hydroxyl-Zahl von 1200 bis 1300 enthalten sind.7. Two-component polyurethane adhesives according to claims 1 to 6, characterized in that diols or diol mixtures with a hydroxyl number of 1200 to 1300 are included.
8. Zweikomponenten-Polyurethanklebstoffe nach den Ansprüchen 1 bis 7, dadurch gekennzeichnet, daß als Diol 1,4-Butandiol enthalten ist.8. Two-component polyurethane adhesives according to claims 1 to 7, characterized in that 1,4-butanediol is present as the diol.
9. Oleochemische Polyole enthaltende Polyolkomponente zur Herstellung von Polyurethanen, dadurch gekennzeichnet, daß in ihr zusätzlich 2 bis 7 Gew.% difunktioneller und/oder trifunktioneller Alkohole oder deren Gemische - bezogen auf das oleochemische Polyol - enthalten sind und daß die Hydroxylzahl der Alkohole oder deren Gemische 1100 bis 1850 beträgt.9. oleochemical polyol-containing polyol component for the production of polyurethanes, characterized in that it additionally contains 2 to 7% by weight of difunctional and / or trifunctional alcohols or mixtures thereof - based on the oleochemical polyol - and that the hydroxyl number of the alcohols or their Mixtures is 1100 to 1850.
10. Oleochemische Polyole enthaltende Polyolkomponente zur Herstellung von Polyurethanen nach Anspruch 9, dadurch gekennzeichnet, daß in ihr zusätzlich Diole oder Diolgemische mit einer Hydroxyl-Zahl zwischen 1150 und 1350 in Mengen von 2 bis 7 Gew.% bezogen auf das oleochemische Polyol enthalten sind.10. oleochemical polyols containing polyol component for the production of polyurethanes according to claim 9, characterized in that in it additionally diols or Diol mixtures with a hydroxyl number between 1150 and 1350 are present in amounts of 2 to 7% by weight, based on the oleochemical polyol.
11. Verwendung von Zweikomponenten-Polyurethanklebstoffen nach den Ansprüchen 1 bis 8 zum Verkleben von starren oder flexiblen Substraten, insbesondere von Kunststoffen, Metallen, Glas oder besonders bevorzugt Holz miteinander oder mit sich selbst. 11. Use of two-component polyurethane adhesives according to claims 1 to 8 for bonding rigid or flexible substrates, in particular plastics, metals, glass or particularly preferably wood to one another or to one another.
PCT/EP1995/000089 1994-01-20 1995-01-11 Two-part polyurethane adhesive with improved adhesive power WO1995020002A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AT95905620T ATE209224T1 (en) 1994-01-20 1995-01-11 TWO-COMPONENT POLYURETHANE ADHESIVE WITH IMPROVED ADHESIVE CAPACITY
EP95905620A EP0740675B1 (en) 1994-01-20 1995-01-11 Two-part polyurethane adhesive with improved adhesive power
DK95905620T DK0740675T3 (en) 1994-01-20 1995-01-11 Two-component polyurethane adhesive with improved adhesiveness
DE59509867T DE59509867D1 (en) 1994-01-20 1995-01-11 TWO-COMPONENT POLYURETHANE ADHESIVE WITH IMPROVED ADHESIVES

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4401572A DE4401572B4 (en) 1994-01-20 1994-01-20 Two-component polyurethane adhesives with improved adhesion
DEP4401572.0 1994-01-20

Publications (1)

Publication Number Publication Date
WO1995020002A1 true WO1995020002A1 (en) 1995-07-27

Family

ID=6508311

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/000089 WO1995020002A1 (en) 1994-01-20 1995-01-11 Two-part polyurethane adhesive with improved adhesive power

Country Status (7)

Country Link
EP (1) EP0740675B1 (en)
AT (1) ATE209224T1 (en)
DE (2) DE4401572B4 (en)
DK (1) DK0740675T3 (en)
ES (1) ES2168352T3 (en)
PT (1) PT740675E (en)
WO (1) WO1995020002A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2335197A (en) * 1998-03-13 1999-09-15 Basf Corp Energy-absorbing elastomers
EP1474283A2 (en) * 2002-02-07 2004-11-10 Huntsman International Llc Cold curable isocyanate adhesives with reduced foaming
US8092632B2 (en) 2007-05-07 2012-01-10 Henkel Ag & Co. Kgaa Method for primerless adhesive bonding of metal or plastics substrates
CN109196061A (en) * 2016-05-31 2019-01-11 阿克佐诺贝尔国际涂料股份有限公司 Double-constituent putty is coated with the substrate of this putty with the method for this putty coating substrate
US10646612B2 (en) 2013-12-20 2020-05-12 Nippon Shokubai Co., Ltd. Polyacrylic acid (salt) water absorbent, and method for producing same

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19546451A1 (en) * 1995-12-13 1997-06-19 Sonderhoff Ernst Fa Two-component polyurethane adhesive precuring to flexible film and curing to tough bond
DE10108025A1 (en) * 2001-02-19 2002-09-05 Henkel Kgaa Two-component polyurethane adhesive for wood materials
ITTO20040255A1 (en) * 2004-04-23 2004-07-23 Rohm & Haas PROCEDURE TO CREATE STRUCTURES CONTAINING URETHANE AND STRUCTURES SO REALIZED
DE102004057699A1 (en) * 2004-11-30 2006-06-01 Henkel Kgaa Two component-polyurethane adhesive (obtained by coating two adhesion compound with cathodic electrode lacquer coated steel sheets and exhibiting a dynamic impact wedge) comprises a polyol component and a polyisocyanate component
US20060276614A1 (en) * 2005-04-12 2006-12-07 Niemann Lance K Bio-based, multipurpose adhesive
US7658974B2 (en) 2005-04-25 2010-02-09 Rohm And Haas Company Process for making urethane-containing structures and the structures made thereby
DE102007012973A1 (en) 2007-03-14 2008-09-25 Henkel Ag & Co. Kgaa Water-permeable stone composite moldings
EP2062927B1 (en) 2007-11-20 2016-06-29 Henkel AG & Co. KGaA 2K-PU adhesive for low temperature applications
US8022164B1 (en) 2010-03-04 2011-09-20 Microvast, Inc. Two-component solvent-free polyurethane adhesives
EP2708565A1 (en) 2012-09-14 2014-03-19 Sika Technology AG Dual component polyurethane compounds on the basis of renewable resources, particularly suitable for use as tough elastic adhesives with adjustable hydrolytic degradability
MX2015009561A (en) 2013-01-25 2015-11-25 Henkel Ag & Co Kgaa Moisture-curing polyurethane composition comprising renewable raw materials.
JP6748732B2 (en) * 2016-03-28 2020-09-02 ダウ グローバル テクノロジーズ エルエルシー Two-component solventless adhesive compositions and methods for making them

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3424766A (en) * 1966-08-03 1969-01-28 Celanese Coatings Co Epoxidized urethane oils
DE3347045A1 (en) * 1983-12-24 1985-07-04 Henkel KGaA, 4000 Düsseldorf TWO COMPONENT POLYURETHANE ADHESIVE
DE4114022A1 (en) * 1991-04-29 1992-11-05 Henkel Kgaa Partially dehydrated castor oil reactive component of poly:ol mixt. - useful for prepn. of solventless 2-component polyurethane adhesive or casting compsns., for coated sheets and plastics, and insulation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3424766A (en) * 1966-08-03 1969-01-28 Celanese Coatings Co Epoxidized urethane oils
DE3347045A1 (en) * 1983-12-24 1985-07-04 Henkel KGaA, 4000 Düsseldorf TWO COMPONENT POLYURETHANE ADHESIVE
DE4114022A1 (en) * 1991-04-29 1992-11-05 Henkel Kgaa Partially dehydrated castor oil reactive component of poly:ol mixt. - useful for prepn. of solventless 2-component polyurethane adhesive or casting compsns., for coated sheets and plastics, and insulation

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2335197A (en) * 1998-03-13 1999-09-15 Basf Corp Energy-absorbing elastomers
US6100363A (en) * 1998-03-13 2000-08-08 Basf Corporation Energy absorbing elastomers
EP1474283A2 (en) * 2002-02-07 2004-11-10 Huntsman International Llc Cold curable isocyanate adhesives with reduced foaming
EP1474283A4 (en) * 2002-02-07 2005-04-20 Huntsman Int Llc Cold curable isocyanate adhesives with reduced foaming
US8092632B2 (en) 2007-05-07 2012-01-10 Henkel Ag & Co. Kgaa Method for primerless adhesive bonding of metal or plastics substrates
US10646612B2 (en) 2013-12-20 2020-05-12 Nippon Shokubai Co., Ltd. Polyacrylic acid (salt) water absorbent, and method for producing same
CN109196061A (en) * 2016-05-31 2019-01-11 阿克佐诺贝尔国际涂料股份有限公司 Double-constituent putty is coated with the substrate of this putty with the method for this putty coating substrate
CN109196061B (en) * 2016-05-31 2020-03-20 阿克佐诺贝尔国际涂料股份有限公司 Two-component putty, method for coating a substrate with such a putty, and substrate coated with such a putty

Also Published As

Publication number Publication date
DE59509867D1 (en) 2002-01-03
PT740675E (en) 2002-05-31
ES2168352T3 (en) 2002-06-16
EP0740675B1 (en) 2001-11-21
ATE209224T1 (en) 2001-12-15
DE4401572B4 (en) 2006-07-06
DK0740675T3 (en) 2002-05-21
DE4401572A1 (en) 1995-07-27
EP0740675A1 (en) 1996-11-06

Similar Documents

Publication Publication Date Title
EP0152585B1 (en) Two-component polyurethane adhesive
EP0764178B1 (en) Use of dimer diol in polyurethane moulded bodies
EP1366132B1 (en) Two-component polyurethane adhesive for wooden materials
EP0740675B1 (en) Two-part polyurethane adhesive with improved adhesive power
EP0937110B1 (en) Use of polyols for isocyanate casting resins and coating compounds
WO2001040342A1 (en) Adhesion promoters for monomer-free reactive polyurethanes
EP0776343B1 (en) Use of polyurethanes with improved resistance to tear propagation as sealants
EP2144945B1 (en) Method for the primerless bonding of metal or plastic substrates
DE2216112C2 (en) Use of compositions based on polyurethanes, which have been obtained by reacting w, w'diisocyanates and diols, as adhesives
EP0260499A2 (en) Use of fatty polyols in the preparation of aqueous polyurethane dispersions
EP0746577B1 (en) single-component polyurethane adhesives
EP2062927B1 (en) 2K-PU adhesive for low temperature applications
DE2105062C3 (en) Process for the production of coatings using two-component polyurethane varnishes
EP0371294B1 (en) Use of polyurethane masses for the production of glass fiber containing laminates
WO1997021748A1 (en) Long-term hydrolysis-stable polyurethanes containing ester groups
DE4041119A1 (en) USE OF MULTIFUNCTIONAL ALCOHOLS TO IMPROVE THE HYDROLYSIS STABILITY OF POLYURETHANES
DE102007052207A1 (en) Modified polyurethane adhesives
DD279582A3 (en) PROCESS FOR THE PRODUCTION OF POLYURETHANE SYSTEMS WITH LONG USE

Legal Events

Date Code Title Description
AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1995905620

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1995905620

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1995905620

Country of ref document: EP